Dye solutions for use in methods to detect the prior evaporation of anhydrous ammonia and the production of illicit drugs

ABSTRACT

Systems and methods providing for the introduction of a dye, particularly a xanthene dye, and more particularly a rhodamine dye, to liquid anhydrous ammonia to discourage theft of the anhydrous ammonia and provide for leak detection in storage vessels. The dye will stain objects which come into contact with the liquid anhydrous ammonia allowing for the detection of such contact. Generally, the staining will be visible to the naked eye, but may also fluoresce when exposed to a particular light source such as ultra violet (UV) light.

CROSS REFERENCE TO RELATED APPLICATION(S)

This application is a Continuation of, and claims priority to U.S.patent application Ser. No.: 10/909,701 filed Aug. 2, 2004 and currentlypending, which in turn claims benefit of U.S. Provisional ApplicationSer. No. 60/491,779 filed Aug. 1, 2003, U.S. Provisional ApplicationSer. No. 60/492,663 filed Aug. 5, 2003, and U.S. Provisional ApplicationSer. No. 60/567,740 filed May 3, 2004. The entire disclosure of all theabove documents is herein incorporated by reference.

BACKGROUND OF THE INVENTION

(1) FIELD OF THE INVENTION

The present invention pertains to additives to anhydrous ammonia as wellas systems and methods for using additives to anhydrous ammonia todetect the prior evaporation of anhydrous ammonia. This detection canindicate leaks in anhydrous ammonia storage vessels and can detect andinhibit the illegal production of methamphetamine.

(2) BACKGROUND OF THE INVENTION

The use and production of methamphetamine is an illegal activity whichimpacts many aspects of American society. Known on the streets as“speed,” “meth,” “chalk,” “ice,” “crystal,” “crank,” or “glass,”methamphetamine has become a substantial drug problem in much of theUnited States in both rural and urban areas. While methamphetamine usewas traditionally associated with white, male, blue-collar workers, thedrug is seeing increasing use amongst teens and other young adults. In anational survey conducted in the year 2000, an estimated 8.8 millionpeople or 4 percent of the population of the United States were believedto have tried methamphetamine.

The drug, which is a powerful stimulant formed from ephedrine orpseudoephedrine, is recognized as causing a powerful stimulant rush, aswell as a pleasurable high of relatively short duration. The high isbelieved to be caused by the release of very high levels of dopamine inthe brain spurred by the drug. Physically, the drug is generally in theform of either a white odorless crystalline powder or a clear crystal.The drug dissolves easily in alcohol and water and can be taken throughvirtually any means including injection, inhalation, ingestion, andsmoking.

While users of methamphetamine are generally pursuing a desirable high,methamphetamine use also has negative toxic effects on the body. Asingle dose can damage nerve terminals in the brain. High doses can alsoelevate body temperature to dangerous, sometimes lethal, levels, as wellas cause convulsions. The drug can be addictive with addicts foregoingsleep and food in pursuit of a high. This addictive behavior can alsolead to an increase in criminal behavior for the addict to obtain theresources to support the addiction. Chronic abuse can also directly leadto psychotic behavior including intense paranoia, visual and auditoryhallucinations, and out-of-control rages that can be coupled withextremely violent behavior. Longer term damage can also includehardening of the brain arteries, mini-strokes and mental disabilities,as well as deterioration of bodily organs.

The production of methamphetamine is also a significant problem for theAmerican public. The production itself is very hazardous involvingnumerous volatile chemicals such as lighter fluid, ammonia, chlorinegas, and others at production “labs” within homes, vehicles, abandonedbuildings and rural structures. These labs regularly explode or catchfire causing property damage and the potential for injury or death. Evenif law enforcement officials have reason to suspect a person or locationis involved in methamphetamine production, they still may have troublelocating a lab or proving a connection as materials may be disposed ofor hidden leaving little, if any, trace of the prior production.

Further, a high percentage of methamphetamine production is carried outby individual users for their own personal use and is performed in smalllabs. Dealers or those manufacturing large quantities of methamphetamineare generally more sophisticated and will often set up labs in moreisolated rural areas far from others where an explosion may causeenvironmental damage and kill the producer, but often will not affectothers unless they accidentally stumble on the lab while exploring thewilderness. Personal labs, however, can actually be more dangerousbecause they are often located in houses, apartments, garages, or evenplaces of business and an explosion or fire from the lab can lead to apotentially dangerous situation placing not the only the users and theirfamilies at risk, but neighbors and emergency personnel who respond.Further, many teenagers or those experimenting in the chemistry ofmethamphetamine may not realize the danger of some of the underlyingingredients which can also lead to a hazardous situation.

Many of the chemicals used in the production of methamphetamine are nowsubject to consumer controls on their purchase as a means to disruptproduction. Because of this, raw materials are often stolen fromlegitimate purchasers or manufacturers. One of the materials used toproduce methamphetamine using a chemical procedure popular in illegalproduction is anhydrous ammonia, a clear liquid which boils (becomingammonia gas) at −28° F. without leaving a trace. Anhydrous ammonia isregularly used by farmers as fertilizer being injected into the fieldsin a pressurized liquid form to improve agricultural production. As manyfarmers and fertilizer dealers therefore need to store and own largeamounts of anhydrous ammonia for this use, farms, as well as fertilizerdealers, anhydrous ammonia transporters, and anhydrous ammonia refiners,have become targets of those who wish to steal the chemical for theproduction of methamphetamine.

In addition to the economic impact of such theft, farmers, fertilizerdealers, transporters, law enforcement and emergency responders may alsobe injured or killed by those attempting to obtain or use the chemicalwho are desperate not to get caught with the chemical (as punishmentsare often quite severe). Further, the theft can have environmentalimpacts as often once the thieves have what they want, they simply allowthe remaining anhydrous ammonia in a storage tank to evaporate into theatmosphere resulting either from their failure to close a valve or fromdamage done to the tank during their theft resulting in a leak. Skincontact with anhydrous ammonia can cause rapid tissue damage andinhalation of ammonia gas can lead to major lung damage and death.Therefore, openly discharging tanks resulting from a completed theft canpresent a major problem to those persons nearby the tanks. Further, theliquid ammonia generally is not transferred by the thief in containersdesigned to store anhydrous ammonia. These improper containers canrupture explosively or leak. Sometimes simply more anhydrous ammoniathan is needed is stolen. Then evaporation may be allowed to occurduring transport to dispose of the excess.

Because of the chemical and physical properties of methamphetamine andthe materials used in methamphetamine production, it is often difficultto detect when an individual is either using the drug, or producing thedrug, unless they are either caught in production, caught with afunctioning lab (or clear indications of a lab), or in a currently highstate. As production and use are often performed in secret or with thosewho will not inform law enforcement, it can often be difficult to detecta person engaged in the drug's production or use during routine lawenforcement activities. Instead, discovery can often require the use ofsearches which can violate Constitutional rights unless law enforcementhas obtained an appropriate warrant. Law enforcement may, however, notbe able to obtain the needed warrant without having already conductedthe prohibited search.

In addition, production of one pound of methamphetamine produces aboutsix pounds of toxic wastes. Lab sites are inundated with these toxicwastes and toxic wastes are often camouflaged, hidden, or buried to tryand prevent their detection. Cleanup costs for each lab are thousands ofdollars and often locating all the wastes in order to clean them up canbe an arduous task. In rural areas, these toxic wastes often contaminatethe soil and water, posing risks to innocent persons who stumble intothese clandestine labs and also to the environment as a whole.

An industrial product related to anhydrous ammonia is ammonium nitrate.Each of these chemicals can be made from the other. Ammonium nitrate isalso used as a fertilizer and has caused its own problems for lawenforcement, particularly since it has been used as a raw material foruse in production of explosives. In recent years, ammonium nitrategained notoriety as a raw material for explosives when it was used toperpetrate a terrorist act against the United States. Further,methamphetamine producers have recently discovered that the material canbe refined in their own production into ammonia suitable for theirneeds.

When examining the methamphetamine culture and its production asdiscussed above, a pervasive element should become clear: those whoproduce methamphetamine fear being discovered. Labs are kept on privateproperty (or in remote areas) where searches by law enforcement aredifficult to conduct and may be unlikely to find the necessary evidenceto carry out an arrest. Further, the acts related to obtaining the rawmaterials are often conducted clandestinely using theft and thirdparties to carry out legitimate smaller purchases to fund a thrivingunderground market in the necessary supplies. Further, methamphetaminelabs use numerous products which have other legitimate uses for which avast percentage of the purchasers utilize them. As the raw materialsused to produce methamphetamine are often indistinguishable from thoseused legitimately, detection of methamphetamine production even afterthe fact can also be difficult.

SUMMARY OF THE INVENTION

Because of these and other problems in the art, described herein aresystems, compositions, and methods for helping to provide indications ofwhen individuals, buildings, vehicles, containers, and other objects,have been around or in contact with either methamphetamine or chemicalsused in its production, particularly anhydrous ammonia. These systems,compositions and methods preclude the need for invasive searches and canpreferably be useful long after the time when any evidence of using orproducing the drug otherwise would be observable.

In an embodiment, the invention provides a method of detecting the priorpresence of liquid-state ammonia including the steps of introducing intoliquid-state ammonia a xanthene dye, the dye creating a stain on amaterial in contact with the liquid-state ammonia upon the conversion ofsome of the liquid-state ammonia from a liquid to a gas; and detectingthe stain. In various alternate embodiments this method provides axanthene dye that is a fluorene, a fluorone, a pyronin, a rhodamine, isrhodamine WT, is fluorescein, or is a dye identified within the range ofindices, 45000-46999, of the COLOUR INDEX, volume 5, ChemicalClassifications, 1976. In an embodiment, the step of detecting the priorpresence of liquid-state ammonia is performed through detection by anunaided human eye. In alternate embodiments, the stain is colored undervisible light illumination, or fluoresces in response to illumination byultraviolet (UV) light. In an embodiment of this method, the xanthenedye comprises between about 1 to 100 parts per million of ammonia on aweight to weight basis.

In a further embodiment, the invention provides a method of detectingthe production of a controlled substance including the steps ofproviding a solution of a xanthene dye in a solvent used in theproduction of the controlled substance, using the solution in theproduction of the controlled substance, thereby generating productionbyproducts that comprise the solution, staining materials contacted byone of the solution, the byproducts, and the controlled substance, anddetecting the staining on the materials, this detection being possibleeven in the absence of any or all of the solution, the byproducts, andthe controlled substance. In various alternate embodiments this methodprovides a xanthene dye that is a fluorene, a fluorone, a pyronin, arhodamine, is rhodamine WT, is fluorescein, or is a dye identifiedwithin the range of indices, 45000-46999, of the COLOUR INDEX, volume 5,Chemical Classifications, 1976. In an embodiment, the step of detectingthe prior presence of liquid-state ammonia is performed throughdetection by an unaided human eye. In alternate embodiments, the stainis colored under visible light illumination, or fluoresces in responseto illumination by ultraviolet (UV) light. In an embodiment of thismethod, the xanthene dye comprises between about 1 to 100 parts permillion of ammonia on a weight to weight basis. In further alternateembodiments the method of detecting the production of a controlledsubstance can be preformed when the controlled substance ismethamphetamine, as well as when the solvent is ammonia.

In a still further embodiment, the method of detecting the production ofa controlled substance includes the step of having the xanthene dyesurvive the production of the controlled substance, thereby staining thecontrolled substance. In an embodiment of this method with theadditional step of having the dye survive the production of thecontrolled substance, the method can be preformed when the controlledsubstance is methamphetamine, and additionally when the xanthene dyeresides on the surface of the methamphetamine. In alternate embodimentsof this method when the controlled substance is methamphetamine, thexanthene dye cannot be washed from the surface of the methamphetaminewith water, acetone, toluene, petroleum ether or xylenes, or thexanthene dye stains materials which come into contact with themethamphetamine. In an embodiment, the staining of the methamphetaminecomprises staining visible to the naked eye. In alternate embodiments,the staining of the methamphetamine is colored under visible lightillumination, or fluoresces in response to illumination by ultraviolet(UV) light.

In an embodiment, the present invention is a solution for detecting theprior presence of liquid-state ammonia comprising liquid anhydrousammonia and a rhodamine dye dissolved in the liquid anhydrous ammonia toform an ammonia solution. In such an embodiment, the rhodamine dye willleave a stain on materials which were in contact with the ammoniasolution upon conversion of some of the ammonia to a gas. In anembodiment of the solution, the stain is a predetermined color visibleto the human eye under illumination by visible light. In an alternateembodiment, the solution is not the predetermined color.

In an embodiment, the present invention is a method of enabling thedetection of the prior presence of liquid-state ammonia including thesteps of introducing a dye into liquid-state ammonia to create a blend,the dye creating a stain on materials in contact with the blend upon theconversion of the ammonia from a liquid to a gas, and storing theammonia and dye in a pressurized tank.

In an embodiment, the present invention is a method for deterring thetheft of liquid-state ammonia including the steps of providingliquid-state ammonia, adding a dye to the liquid-state ammonia; andforming a solution of the ammonia and the dye, the solution generating astain on objects that contact the solution. In such an embodiment, thestep of forming a solution includes forming a homogeneous mixture.

In alternate embodiments, the stain is only detectable upon evaporationof the ammonia from the solution, the solution is visibly distinct fromthe liquid-state ammonia, the liquid-state ammonia comprises anhydrousammonia, and the dye comprises one of a colored dye, a fluorescing dye,a xanthene dye, a rhodamine dye. In an embodiment wherein theliquid-state ammonia comprises anhydrous ammonia, the anhydrous ammoniais stored under pressure.

In an embodiment, the present invention is a method of deterring thetheft of anhydrous ammonia including the steps of providing a sealedcontainer of anhydrous ammonia, and affixing a label to the sealedcontainer, the label indicating that the anhydrous ammonia includes adye that will leave a detectable stain on objects that contact theanhydrous ammonia but which is not readily visible in the anhydrousammonia, but wherein the anhydrous ammonia does not include theindicated dye. In an alternate embodiment, the label indicates that theanhydrous ammonia includes a dye that will stain a controlled substanceproduced using the anhydrous ammonia.

In an embodiment, the present invention is a method of inhibiting theuse of a controlled substance including the steps of providing asolution of a dye in a solvent used in the production of the controlledsubstance, using the solution in the production of the controlledsubstance, having the production stain the controlled substance, andinhibiting use of the controlled substance due to a decreased desire touse the controlled substance when stained as compared to the controlledsubstance absent the stain. In an embodiment, the stained controlledsubstance is able to stain materials contacted by the stained controlledsubstance. In a further embodiment these materials include human skin.

In an embodiment, the present invention is a method of detecting theprior presence of ammonium nitrate including the steps of introducingonto the surface of ammonium nitrate a xanthene dye, staining materialscontacted by the ammonium nitrate, and detecting the stain. In a furtherembodiment, the dye remains in ammonia produced from the ammoniumnitrate. In various alternate embodiments this method provides axanthene dye that is a fluorene, a fluorone, a pyronin, a rhodamine, isrhodamine WT, is fluorescein, or is a dye identified within the range ofindices, 45000-46999, of the COLOUR INDEX, volume 5, ChemicalClassifications, 1976. In an embodiment, the step of detecting the priorpresence of ammonium nitrate is performed through detection by anunaided human eye. In alternate embodiments, the stain is colored undervisible light illumination, or fluoresces in response to illumination byultraviolet (UV) light.

BRIEF DESCRIPTION OF THE DRAWINGS

The patent or application file contains at least one drawing executed incolor. Copies of this patent or patent application publication withcolor drawing(s) will be provided by the office upon request and paymentof the necessary fee.

FIG. 1 shows an exemplary drawing of a household methamphetamine labwith indications of staining on various items resulting from anembodiment of the invention.

FIG. 2 shows a color photograph of a coffee filter includingmethamphetamine stained pink from being produced using anhydrous ammoniaincluding a rhodamine dye.

FIG. 3 shows a color photograph of a stain down the side of an anhydrousammonia nurse tank. Anhydrous ammonia including a rhodamine dye is shownleaking at the top.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT(S)

Discussed herein are systems and methods, as well as dyes, which can beused with liquid anhydrous ammonia or other ammonia products orprecursors, which provide for the detection of the conversion of liquidammonia to gaseous ammonia. In this application the term ammonia willgenerally refer to compositions that are primarily ammonia (NH₃),particularly as distinct from a solution of ammonia in water, which iscommonly referred to as ammonia. In this application a solution ofammonia in water or any other liquid will be identified as such asolution. The use of the term ammonia herein encompasses anhydrousammonia, particularly liquid anhydrous ammonia, including the industrialproduct produced and sold in a commercial grade on a bulk scale fornumerous applications, particularly as an agricultural fertilizer.Commercial grade anhydrous ammonia typically has a water content of lessthan 0.5%, with water being the greatest impurity, and the ammoniaotherwise being greater than 99.5% pure. The term liquid ammonia as usedin this application refers to ammonia in the liquid state, otherwisetermed liquid-state ammonia.

Liquid and gaseous ammonia are generally clear and colorless with thegas having a characteristically pungent smell. Ammonia has a boilingpoint of −28° F. and a freezing point of −107.9° F. This means that atordinary indoor and outdoor temperatures ammonia is a gas. In commercialapplications, however, ammonia is typically stored and transported inspecialized containers under pressure, so that even at normaltemperatures it can be maintained as a liquid. Once the pressure isreleased, if the temperature is greater than −28° F., liquid ammoniawill boil. After the boiling or evaporation of liquid ammonia from asurface and the dissipation of the resulting gas, the prior presence ofthe ammonia will generally not be detectable.

In general, there are discussed herein marker or tracer dyes which canbe placed into liquid ammonia, or precursors or products of ammonia,such as, but not limited to ammonium nitrate, that provide for stainingof surfaces and other materials which come into contact with the liquidammonia, or ammonia precursor or product. As used herein the term dyeencompasses compositions more commonly referred to generally ascolorants or pigments. Concerning liquid ammonia, it is generallypreferred that this staining become apparent after the evaporation orboiling of liquid ammonia, which converts the liquid to a gas. Furtherregarding liquid ammonia, it should be recognized that the stainingcaused by the compositions, systems, and methods discussed herein isparticularly useful in the detection of at least two events. A firstevent is the unintended release of liquid ammonia due to tank leaks orsimilar problems in legitimate and legal uses of ammonia. A second eventis the illegal acquisition and use of liquid anhydrous ammonia,particularly in the production of methamphetamine.

Anhydrous ammonia is highly corrosive, and therefore toxic. Legitimateusers will generally try to avoid exposure to the liquid and gas toprevent danger to themselves, others, and the environment. For safetyreasons, having an indication that ammonia evaporation or boiling isoccurring or has previously occurred serves the purpose of detecting anunintended release that needs to be remedied. Further, indications of anunintended leak in a legitimate use can provide information of apotential danger to emergency responders and enable a successfulevacuation of an area if necessary. As the tanks used to store anhydrousammonia are often converted to use for storage of propane, similarsituations may arise with respect to unintended leaks of propane fromsuch tanks. In these situations, as with ammonia, a dye placed into thepropane can be similarly beneficial.

Detection of the evaporation or boiling of liquid ammonia in the secondevent, illegal acquisition or use of ammonia, will generally occurbecause those persons illegally acquiring or using ammonia, typicallymethamphetamine producers, generally lack the necessary sophisticatedliquid anhydrous ammonia handling equipment or lack the skill orpatience to use it properly. Thieves, methamphetamine producers, andconspirators therewith are likely to be exposed to evaporating orboiling ammonia as the ammonia is released from a pressurized storagecontainer during transfer to a thief's container, and during other usesof the ammonia by a thief or a conspirator or a methamphetamineproducer, such as in the synthesis of methamphetamine. Detection of suchan illegal event will generally be possible because dye stains remainingafter ammonia boiling or evaporation will occur on objects and inlocations where it is improbable that the ammonia was being usedlegitimately.

In a first embodiment, the compositions, systems, and methods relate tochemicals, specifically dyes, which may be placed in ammonia or can beadded to (such as by surface spraying) ammonia precursors or products(such as solid ammonium nitrate) and which are non-volatile, such thatthe dyes will remain on contacted surfaces during boiling, evaporation,or sublimation of ammonia, its precursors, or products, and will stainthose surfaces. It is preferable that the dye stain the objects presentduring, and the products of, the production, transportation,containment, or use of ammonia where such steps result in uncontrolledboiling or evaporation of ammonia.

While a plethora of dyes may be used in detecting the evaporation orboiling of liquid ammonia, it is preferred that the dye have certaincharacteristics. The dye is preferably soluble in liquid ammonia. Thedye preferably does not react with ammonia in a way that degrades thedye, or at least its ability to stain. The dye preferably will stainnon-porous, porous, or semi-porous substances, particularly those usedfor storage of ammonia and those used in the production ofmethamphetamine (for instance, plastics, paper, human skin, andclothing), as well as those substances likely to be in the environmentof a methamphetamine production lab, such as wallpaper, carpet, cement,dry wall, and wood. The dye will also preferably be relatively easy toremove from the skin and other washable surfaces to an extent that itcannot be easily detected by unaided sight, since the absence of suchwashability may impede lawful uses of anhydrous ammonia. A preferred dyewill be relatively difficult to remove from such materials and surfaces,however, to levels below the detection limit of other non-invasivedetection methods. The preferred dye will also be generally safe withrespect to human and animal health, including to exposures such asingestion and skin contact, and with respect to the environmentgenerally. That is, a preferred dye can be safely placed into soil whenan anhydrous ammonia solution of dye is used as fertilizer. It isfurther preferred that the dye be sufficiently stable so as to bemaintained at operative concentrations in liquid ammonia at all timesprior to evaporation of the ammonia. That is, in a preferred embodiment,the dye can be maintained in liquid ammonia in all forms of storage andtransportation devices, including those that are improvised and used forillegal purposes (including modified propane tanks and food gradethermoses and coolers), until evaporation of the anhydrous ammoniaoccurs. Additionally, for reasons discussed further below, the preferreddye will be difficult to remove from ammonia either before or during theproduction of methamphetamine, thus, allowing the dye to carry into thefinal methamphetamine product. Xanthene dyes, particularly rhodamines,have most of these preferred properties.

In an embodiment, it is further preferred that the dye is stable to orgenerated or regenerated during the process of converting ammoniumnitrate to ammonia, such that the dye could be placed on solid ammoniumnitrate, and remain in any liquid ammonia or ammonia gas derived fromthat ammonium nitrate. In such an embodiment, when the dye is placedwith ammonia nitrate, the dye may also stain objects which come intocontact with the solid ammonium nitrate.

In a preferred embodiment, the dye selected is a xanthene dye such as afluorene or flourone. The class of xanthene dyes is a well known classof dyes containing a xanthene backbone, as shown below in structure (1),which may be substituted at numerous positions, replacing the indicatedhydrogen atoms with one or more substituents that may be simple (such asan atomic moiety) or complex (such as a molecular moiety). According tothe Society of Dyers and Colourists and the American Association ofTextile Chemists and Colorists, as published in their work, COLOURINDEX, volume 5, Chemical Classifications, 1976, the entire disclosureof which is herein incorporated by reference, the xanthene dye class iscovered by colour indices 45000-46999. While the COLOUR INDEX is notexhaustive in listing xanthene dyes, or any other dyes in any otherclass, it provides a general reference for industrially significant dyesin the various classes and thereby also provides a source for classdefinitions.

The selected dye is more preferably a pyronian, and still morepreferably a rhodamine. In alternate embodiments, the dye is rhodamineWT (2) (also known as Acid Red 388) or fluorescein (3) (also known asAcid Yellow 73). Both of these dyes are commonly used

as fluorometric tracing dyes, particularly in waterways, are consideredenvironmentally safe, and have strong fluorescent properties whenexposed to ultraviolet (UV) light. It should be understood, however,that any xanthene dye could be used in alternative embodiments of theinvention, especially those dyes capable of being dissolved intoanhydrous ammonia in amounts of about 1 to 100 parts per million on aweight to weight basis (ppm w/w).

In further embodiments, other dyes used as fluorometric tracing dyeswith strong fluorescent properties (including aminoketones such asLissamine FF) could be used, as they will often have similar propertiesand operate in a similar way to xanthene dyes when placed in liquidammonia. As well, other types of dyes, such as, but not limited to, vatdyes, fluorescent dyes, food dyes, clothing dyes, or hair dyes,particularly those which are hydrophilic, may be used. Inks, pigments,or other materials which provide coloration (encompassed herein withinthe definition of dye) can also be used in alternative embodiments, ontheir own or in conjunction with the other dyes discussed above. All ofthese dyes will result in indications of the presence or prior presenceof liquid ammonia. Certain dyes, however, particularly xanthene dyesthat contain no large halogen atoms, are preferred due to theirfluorescent properties, resulting in detectablity even in minutequantities. Further, xanthene dyes such as rhodamines are generally notvisible in the liquid ammonia under illumination by visible light, andonly express coloration upon evaporation of the liquid ammonia.

While the dyes discussed above generally provide for visual detectionwhen they stain contacted materials, either directly by coloring anobject or indirectly such as through fluorescence, visual detection isby no means required. In other embodiments, the fluorescence emission isnon-visible. In still further embodiments, dyes or tracers which emit,absorb, or reflect other signals such as x-rays, particles, infrared(IR) or ultraviolet (UV) emissions, audio signals, ultrasonic signals,or any other form of detectable signal, can alternatively oradditionally be used to detect the presence or prior presence ofammonia, or a precursor or product thereof.

In an embodiment of the invention, the ammonia is “dyed,” i.e., providedwith the ability to leave behind a stain, by simply intermixing thexanthene dye into the liquid anhydrous ammonia. In a preferredembodiment, the intermixing results in the dissolution of the dye in theliquid ammonia, including when the intermixing is of a dye solution andliquid ammonia that results in the dye remaining in solution. As usedherein, dissolution means the creation of a homogeneous mixture eitherby true solvation or by another physical mechanism such as the creationof a suspension. At or after dissolution, the liquid ammonia solution isthen exposed to objects and materials that will be stained during theevaporation or boiling process. As the ammonia solution boils orevaporates, the staining effect of the dye remains on the surface fromwhich the liquid ammonia departs. Through the remaining stain, the priorpresence of liquid ammonia on that location is detectable.

In a preferred embodiment, the dye is added in such quantities to liquidammonia that the dye is not visible or is only slightly visible to thehuman eye when the dye in ammonia solution is illuminated with light inthe visible spectrum (about 400-800 nm). (Note that illumination bylight in the visible spectrum is considered a normal lighting conditionas this is provided by sunlight and white electric lights, forinstance.) In an alternative embodiment, the liquid ammonia solution ofthe dye is obviously colored with a dye that is visible to the human eyeunder illumination by light in the visible spectrum. In either case, thesolution of ammonia and dye can then be used as ammonia typically wouldbe used under circumstances in which no dye was dissolved in theammonia.

In further embodiments, the stain remaining after evaporation or boilingof the ammonia may be or may not be visible under visible lightillumination, regardless of the coloration of the dye in ammoniasolution. A generally non-visible stain generally eliminatesinconvenience in lawful uses of ammonia resulting in staining. In eithercase, where the stain is only expressed upon evaporation or boiling,hoses, containers, and other devices used in containing ammonia and inwhich no boiling or evaporation is intended to occur are generally notstained. Where the stain is only expressed upon evaporation or boiling,the presence of the stain usually indicates an unintended or an unlawfulrelease, which are the types of release generally of interest.

The amount of dye which is added to ammonia can, in many cases, be quitesmall and still produce the effects discussed above. It is generallypreferred that the concentration be between about 1 and 100 ppm w/w ofdye in liquid anhydrous ammonia. This concentration results in the dyecomprising a quite small concentration in the soil for a typicalfertilizer application. (In a typical fertilizer application, ammonia isapplied at a rate of about one ton per eight acres. Assuming an evenapplication depth of one foot, and a consistent soil density of 40 lbsper cu. ft., 13,939,200 lbs of soil are treated by a ton of ammonia.Assuming a 10 ppm w/w concentration of dye in ammonia, the soilconcentration of dye is about 1.4 parts per billion on a weight toweight basis (ppb w/w).) These relatively small amounts of dye inammonia can still result in impressive staining of materials asdiscussed in the Examples section and shown in the figures. In fact,small amounts of dye are often actually more effective at staining,particularly fluorescent staining, since as a result of self quenching,high concentrations of a fluorescent dye may have a reduced fluorescencecompared to lower concentrations.

For the purposes of the rest of this discussion, it will be presumedthat a rhodamine dye, particularly rhodamine WT, is used as the dye. Oneof ordinary skill in the art, however, would understand how thediscussion below could be adapted for use with other dyes that areindicated above.

Rhodamine WT is a preferred dye because of its numerous propertiesuseful for detecting the presence or prior presence of ammonia, orprecursors or products thereof. Useful properties include that rhodamineWT is visibly colored a shade of red (under visible light illumination)as well as being fluorescent. Rhodamine WT has strong fluorescentproperties, generating significant quantities of visible spectrum lightof a red or pink color upon irradiation with ultraviolet light, even forsmall amounts of the dye. This fluorescent property makes likely thedetection of a stain on various surfaces, even for small amounts of thedye, such as amounts that are possibly not even visible under normalvisible light illumination. Additionally, the dye is non-volatile, so itwill remain on the stained object under normal temperature and pressureconditions. A further useful property of rhodamine WT is that the liquidammonia solution of the dye is not, itself, obviously colored red orpink. The dye in solution is not readily apparent under visible lightillumination as it does not cause significant discoloration of theliquid ammonia, though a slight yellowing may be present. Still further,rhodamine WT is commonly used as a water tracing dye. It has been addedto the environment by professionals in fairly concentrated form in thepast and will continue so to be, thus indicating a determination as tothe dye's fairly high safety level with respect to animal andenvironmental health. Still further, rhodamine WT embodies the preferredproperty that the dye be able to survive the production ofmethamphetamine so as to stain the resultant drug product. In this way,all facets of the drug's production, transport, and use pose a potentialstaining risk, which makes all of these activities more likely to bedetected.

In an embodiment, the staining by an ammonia solution of rhodamine WToperates as follows. When the ammonia is converted from a liquid to agaseous state (which certainly occurs at temperatures of −28° F. andabove under normal pressures) the dye is left behind on the surface fromwhich the ammonia boiled or evaporated because the dye is not volatile.In accord with rhodamine WT's natural properties (mentioned above) thestain generally is visible as a red stain under both visible and UVlight irradiation. Thus, an ammonia solution of rhodamine WT will stainobjects exposed to the solution or the vapor thereof (which vaporcontains a mixture of both liquid droplets and gaseous ammonia) uponevaporation or boiling of the ammonia. Materials that may be stained inthis way include, but are not limited to, papers, clothing, textiles,and human skin. The rhodamine WT stain will also fluoresce a pink or redcolor when exposed to ultraviolet light.

The staining effect of the solution of dye in ammonia, as discussedabove, is particularly useful with regard to legitimate uses of ammonia,particularly as when a liquid anhydrous ammonia tank develops a leak.When such a leak occurs in a tank holding the dye and ammonia solution,the tank and nearby objects will rapidly become stained near the leakpoint as liquid or vapor will be forcibly ejected from the tank underpressure. In an embodiment, staining is visible to the naked eye undertypical visible light irradiation, such as by the sun or normal whiteelectric lights. Such visibility is particularly preferred as itprovides an immediate indication of danger and allows for an emergencyresponse to be initiated immediately if need be. The staining provides aquick indication that the tank needs to be repaired. Further, if a leakshould occur in a pipe, tank, or any other structure being usedlegitimately, the user will have near immediate indication of the leak,and can shut down machinery or institute additional containment measuresto prevent death or serious bodily or environmental injury. Suchdetection of unintentional releases is a particularly valuable benefitbecause the dye can remain in the liquid ammonia at all stages ofproduction and use of the ammonia, so such detection is availablethroughout the stages of production, storage, and use. Note that the dyeis not introduced into an empty tank to try to detect leaks, but ratheris present when there is liquid ammonia in the tank (or other storage ortransport device) and therefore can stain the tank if a leak develops atanytime there is liquid ammonia in the tank. This is the same time whena tank leak creates a danger to persons and the environment. FIG. 3shows a picture of a leaking valve on an anhydrous ammonia nurse tank.The white cloud of ammonia gas is seen towards the top valve of thetank, but would clearly not be easily seen from a distance; the twostreaks of pink, however, from a rhodamine WT dye, on the white surfaceof the tank are immediately apparent.

In addition to the general detection of the presence or prior presenceof ammonia, as discussed above particularly with respect to detection ofunintentional releases in legitimate uses, the inclusion of a dye inanhydrous ammonia can serve in many ways to help combat the majorsocietal problems related to methamphetamine production and use. Withrespect to persons producing and using methamphetamine, and personstrafficking in ammonia for illegal purposes, the solution of dye inammonia is a substantial aid in identifying these individuals. Withrespect to law enforcement and emergency responders who first appear ona scene where methamphetamine production activities have been takingplace, the staining that results from a solution of dye in ammonia is asubstantial aid in identifying the hazardous nature of the scene. Withrespect to taking steps broadly toward eradicating these societalproblems, the solution of dye in ammonia is a substantial deterrent toboth the production and use of methamphetamine. Further, as theft ofanhydrous ammonia and leaks in storage tanks often go hand-in-hand, thedetection of theft can also help prevent additional damage from a leakas a result of that theft.

The staining effect of the solution of dye in ammonia can facilitate theidentification of producers and users of methamphetamine andconspirators therewith, both by direct and indirect methods. Asdiscussed above, the dye in ammonia solution will stain materials andsurfaces from which the ammonia evaporates. In this way anyone using ortransporting the ammonia has the potential to be contacted, particularlyon their skin or clothing, by ammonia and stained when it boils orevaporates. In an embodiment, the dye may also stain the end productmethamphetamine, which may in turn stain the person selling the productor the person using the product when they come into contact with it. Itis the stain on the skin of individuals involved with methamphetamineproduction and use that leads to their direct identification. For such ause, it is preferred in an embodiment that the staining be visual to thenaked eye under typical visible light irradiation, such as by the sun ornormal white electric lights. Such visibility allows for detection by aplethora of parties.

In an indirect sense, producers and users of methamphetamine andtraffickers of ammonia will be identified through the staining effect ofthe solution of dye in ammonia on objects and materials other than skin.The staining effect can help identify the presence or prior presence ofliquid ammonia and other products used in the illegal manufacture ofmethamphetamine in vehicles and buildings, and on containers andclothing, as well as other objects nearby. This staining will provideevidence to help in the identification and prosecution of those involvedwith methamphetamine since those persons who own or have a right to useor can otherwise be connected to the property that was stained will beimplicated as potential wrongdoers. Depending on the nature of thedetection, the presence of a stain may be sufficient grounds to justifya more invasive search, the arrest of a suspect, or confiscation ofcertain goods, such as for further testing.

For example, a routine traffic stop can allow law enforcement personnelto detect that the driver or occupants recently were exposed toanhydrous ammonia, possibly warranting a further search of the vehicleor potentially providing sufficient grounds to obtain a search warrantof a home. While a visibly colored stain would make such detectionsimple, where the stain was not visible, a fluorescent stain could bedetected by shining an ultraviolet light on a suspect. Investigation byUV light is a non-invasive procedure that is performed with fairlycommon technology which may make such searches by police reasonable.Such searches may allow law enforcement on routine business to detectthat an individual may have had recent contact with anhydrous ammonia,ammonium nitrate, or methamphetamine. Law enforcement may also shine UVlights on vehicles or on dwellings or other locations from a distance toperform other noninvasive searches.

In further examples, neighbors, landlords, garbage collectors, servicepersonnel, school officials, club bouncers or anybody else havingcontact with an individual may see indications of the staining from asolution of dye in ammonia and contact law enforcement or take otheraction. In particular, night clubs occupy the convenient coincidence oflocations where methamphetamine likely may be used and there is often apresence of UV lights for other legitimate uses. UV lights are typicallyused as a method to determine paying customers or customers over aparticular age (such as the legal age for alcohol consumption) throughtheir use in combination with a fluorescing chemical hand stamp or maybe used for environmental light effects. Under circumstances of typicalultraviolet light use in these settings, a club owner or bouncer maydetect that an individual may have been in contact with methamphetamineor involved in its production, either in the club or prior to enteringthe club, and can alert law enforcement or take other responsiblemeasures. In all of these ways, both direct and indirect, theidentification of those involved in methamphetamine production becomesmore easily obtainable.

Just as for the situation where a hazardous ammonia leak is detectedthrough staining in an unintentional release in a legitimate use ofammonia, where illegal uses and trafficking are involved, the indicationof the presence or prior presence of ammonia at a site where it wouldotherwise not be expected is likely to indicate hazardous conditions,due for instance to the presence of liquid ammonia or to other chemicalsand apparatuses related to methamphetamine production, all of whichpresent multiple health hazards. Where the stain is not obvious undervisible light illumination, but is fluorescent, UV lights can be used bycleanup crews or crime scene units to locate evidence and dispose ofcontaminated articles.

An indication of the staining properties of an embodiment of the presentinvention is shown in FIG. 1, where stains (265) are shown that would bean aid to both identifying individuals involved and identifying thehazardous nature of the location. In this exemplary embodiment, asolution of dye in ammonia was used in a clandestine methamphetamine lab(201) and has stained various items that were in contact with the liquidanhydrous ammonia which has since evaporated. The vessel (203) and thevessel's lid (213) used to transport the liquid ammonia and dye solutionhave been stained (265). Also as a result of a spill from or escapingvapor from the vessel (203), the floor (215) is stained (265). Escapingvapor or a spill has also stained (265) a user (211) of the dye inammonia solution, as well as the user's clothes (229). Further, itemsused in the lab such as ajar (213) and the pipe (219) used inconjunction with a two-liter bottle (217) as part of the saltingprocedure are stained (265). Each of these also released vapor or liquidstaining (265) the stove (207), counter (209) and table (205).

Because of all the above staining properties, the inclusion of a dye inliquid ammonia makes the production and use of methamphetamine a messierendeavor and one more likely to be detected. This messiness andincreased detectability resulting from the solution of dye in theammonia leads to significant deterrent effects on those who wouldotherwise be involved in methamphetamine production and use. Thedeterrent effects include psychological deterrence, physical deterrence,and economic deterrence.

The psychological deterrence comes from a decreased willingness toparticipate in activities related to methamphetamine production and usedue to the desire not to be stained personally or have one's possessionsstained and a distaste therefore, as well as an increased fear of beingidentified and prosecuted for these activities. Since the staining maycome from either the dye in the ammonia solution itself during stealing,transportation, or use thereof, as well as from methamphetamine stainedas a result of a production using a dye in ammonia solution, all personsinvolved in activities related to methamphetamine production and use maybe deterred. To take advantage of this psychological deterrent effect,warning signs may be used to indicate that certain stored ammoniaincludes a tracer dye. Such warning signs may be used as a deterrent toillegal acquisition of the ammonia or dye in ammonia solution so labeledwhether or not the dye is actually present in the ammonia in thecontainer so labeled, and whether or not the dye is visible in ordinaryillumination such as sunshine or white electric lights. Thepsychological deterrent effect may be present in any number of specificcircumstances in which one decides not to make, use, transport, orotherwise be in contact with liquid ammonia, liquid ammonia including adye, or a product such as a drug made therefrom.

A methamphetamine producer needs to engage in elaborate protectionmethods to prevent the dye from being readily apparent on themselves,and objects and materials that come into contact with a dye in ammoniasolution, including their own personal and real property. Manymethamphetamine producers will not or cannot take such precautions.Because the precautions to reduce the risk of staining from use of a dyein ammonia solution may be costly or time consuming or otherwiseinconvenient, a person who would otherwise be a methamphetamine producermay decide not to produce methamphetamine or may produce the drug byalternative methods which may be less reliable, take more time, andproduce an inferior product. This is an example of an embodiment of thedeterrent effect on methamphetamine producers. In another embodiment,while not a complete deterrent, if a methamphetamine producer decidesnot to produce the drug in their residence for fear of detection by alandlord or someone else, and instead produces in a remote area with alow population density, an alternate benefit is obtained by the generaldeterrent effect of staining, which is greater safety for neighbors nearthe location of the producer's residence, and potentially greater safetyfor emergency responders, who face a less confined hazardous site whenthe remote production lab is discovered.

Further, because in an embodiment the methamphetamine product isstained, it is readily apparent to a potential user that the tracer dyecould be transferred to them through use of the methamphetamine producedusing the dyed anhydrous ammonia. FIG. 2 provides a coffee filterincluding stained end-product methamphetamine. Such staining capabilitymay deter purchase or use of the stained methamphetamine. In an example,a teenager at a party may be willing to try unstained methamphetaminewith the expectation that by the time they return home all evidence oftheir use will have disappeared, but that same teenager likely will bemuch less willing to try the same drug when, for instance, use of itwould be easily detected by their parents the next morning due to thestaining effect of the drug and the generation of a stain on theteenager's person or the teen's clothes. In this case, the willingnessto use the drug or lack thereof is a measure of psychologicaldeterrence.

Such a deterrence may occur even if the drug is not visibly stained, andwhether or not it is stained at all. It is possible for the deterrenceto effect a potential user's decision to use on the basis that the drugis believe to be stained with a non-visible but fluorescent dye. It isalso possible that a potential user would be deterred simply from thepossibility that the drug is stained and choose not to use, regardlessof whether the user believes the drug is stained.

In another example, the staining of solvent carriers of themethamphetamine product, such as water or alcohol, can deter theintroduction of the drug to a person's beverage without their knowledge,particularly where the staining results in visible coloring. This canprevent people from accidentally becoming addicted to the drug insituations where the drug is ingested without that persons knowledge,such as where the drug is placed in that person's drink by anotherperson. This can also prevent the drug from being used to “dope” otherswithout their knowledge, such as in the common use of the so-called daterape drug. Such unknown doping also occurs through the mixing of illicitdrugs, for example, when methamphetamine is mixed with cocaine. Stainedmethamphetamine will also discourage use of the drug as users aredeterred from use by the obvious discoloration. Besides the increasedrisk of detection (even long after use), such discoloration raisesconcern regarding the quality of the product. Where the pure product isknown to be white, a potential user may wonder what other impurities,possibly harmful impurities, may be present in a stained drug product.This change in appearance is also shown in FIG. 2.

For the ammonia trafficker, the staining effect of the vapor, makes itmore difficult to initially obtain the liquid ammonia if one does notwish to be stained. As most thieves of liquid ammonia do not have accessto sophisticated safety and transport equipment such as is used byauthorized users, it is likely that while attempting to steal the liquidammonia, liquid streams, droplets, vapor, or mist will be released underpressure from the tank, staining the would be thief, their clothing, thetransport vessel and associated items, often including a vehicle inwhich the stolen liquid ammonia is being carried. Where the stain isobvious under visible light illumination, this stain may be readilydetected by law enforcement as the thieves are making their getaway withthe liquid ammonia, allowing them to be apprehended before they can sellsuch stolen ammonia, or even begin methamphetamine production. Inanother embodiment, the dye in ammonia solution is not obviouslycolored, so that it is unapparent to one who would attempt to steal theliquid ammonia that the material may or may not contain the dye until itis too late and the staining has occurred. Such an embodiment deters thetheft of all anhydrous ammonia as there exists in the generalconsciousness of would be thieves a fear of potential staining, even ifthe dye is not included in solution.

In addition to making the production and use of methamphetamine amessier process, and thereby providing a psychological deterrent to suchactivities, in an embodiment, the inclusion of a tracer dye such asrhodamine WT in anhydrous ammonia will also make the production ofmethamphetamine more time consuming and costly, either by decreasing theresultant yield of methamphetamine produced using the solution of dye inammonia, decreasing the resultant quality of methamphetamine, loweringits market price, or increasing the time and materials required to makethe same amount of the same quality of methamphetamine as would beproduced using pure liquid ammonia. The inclusion of rhodamine WT, otherxanthene dye, or other dye may inhibit the necessary reactions requiredto form methamphetamine. Also as presented below in the Examples sectionwith respect to rhodamine WT specifically, methamphetamine produced fromammonia including a xanthene dye is a product dissimilar in physicalcharacteristics from methamphetamine produced without the dye present.Not only is the produced methamphetamine colored instead of white, butit is also not a flowable powder and is instead wet or oily. The step inproduction that would normally result in an essentially dry, white,powder within a few minutes, instead results in a gooey or gummy pinkmass taking increased time and effort to filter when methamphetamine ismade using a solution of rhodamine WT in ammonia. This wetness or oilycharacter makes the drug product unappealing, difficult to manipulate,collect, and carry, and may alter the procedure by which one uses thedrug to obtain the desired physiological effect. It may also inhibit thedesired physiologic effect to some extent, as well. These results in thesynthesis of methamphetamine when a solution of dye in ammonia is usedresult in physical deterrence through reduced or eliminated yields, oreconomic deterrence through more costly procedures required to obtain“clean” product, if such a result is possible after the stained productis produced. As discussed above and in Example 1 below, even smallamounts of dye result in significant alteration of the characteristicsof the methamphetamine produced. Because such small amounts result insuch alteration, it may be particularly challenging to remove the dyefrom the ammonia to an extent that the dye does not interfere with thephysical properties of the methamphetamine.

An additional result of the various deterrent effects of a dye inammonia solution, is a certain security provided to those wholegitimately store, transport, and use liquid ammonia. With knowledgethat tanks may contain marking dye, someone who would steal from alegitimate user is more likely to find an easier target to steal from,or forego use of ammonia, to use a different product or materialaltogether, and in this way avoid the problems associated with detectionof wrongful activity. This deterrent, then, eliminates either or both ofthe financial drain and bodily danger to legitimate users.Alternatively, while the staining may not deter completely certainthefts of ammonia, it may force those attempting such thefts to use moresophisticated methods, which are generally safer for everyone involved,including the victim, the thief, and those nearby. Further, in so muchas there is benefit to knowing about a theft or attempted theft, thevisible color staining of an embodiment, in particular, is an aid tolegitimate user victims of theft. Rather than having to wait until ameasurement indicates less ammonia present in a storage tank thanexpected, the victim of a theft is likely to know of the theftimmediately upon viewing the area around the tank, due to the coloredstain at the site of the theft. To the extent it is beneficial, a victimcan even identify a theft or attempted theft from a distance due to thecolored stain.

The addition of a dye to solid ammonium nitrate can also serve similarends as those served by the dye in ammonia solution, that is,identification of individuals and hazardous conditions involved withmisuse of the material. As well, deterrence in other circumstancesrelated to the production of illicit drugs, such as where an attempt ismade to convert ammonium nitrate to ammonia for use as described above,and in unrelated circumstances, such as the production of explosives.For example, those attempting to build explosives or bombs out ofammonium nitrate may be stained, which can facilitate the recognitionand disruption of possible terrorist activities before they can becarried out. Further, a dye in ammonium nitrate can stain thoseattempting to convert the ammonium nitrate into anhydrous ammonia fortheir use in later methamphetamine production. While the dye may remainin the resultant ammonia product, providing all the benefits discussedabove, one would see that even if it does not, dying of the ammoniumnitrate can provide for a deterrent effect based on a staining effectcaused by contact with the ammonium nitrate.

As a benefit essentially opposite of deterrence, where the presence ofthe stain is unknown and not visible under sunlight or white electriclights, but yet detectable, such as by fluorescence, there is provided afalse sense of security to those who use a solution of dye in ammonia orillicit drugs produced therefrom. The benefit to society is in the factthat these users are now easier to detect because they are not highlyalert and sensitive to potential detection.

The compositions, methods, and systems discussed herein are particularlyuseful with respect to solutions of dyes in ammonia to detect thepresence or prior presence of ammonia. A reason for such particularutility is that a primary use of ammonia is as a fertilizer foragricultural production. In such an application it is fairly irrelevantif the land comprising a field used to grow agricultural products hasapplied to it a small quantity of a dye, so long as the dye isrelatively safe with respect to animal and environmental health. Whilethe compositions, methods, and systems disclosed herein are also usefulwith respect to solutions of dyes in other solvents such as alcohols,ethers, ketones, and other organic or inorganic solvents, especiallythose solvents that may be used in the production of controlledsubstances other than methamphetamine (i.e., substances regulated byfederal law, such as are listed in Title 21 of the Code of FederalRegulations), or in other production methods for methamphetamine thanthe lithium reduction method, which relies on ammonia as a solvent, suchother solvents are often used for purposes in which the presence of adye is unwanted and perhaps detrimental. In sum, there is no reason thatthe compositions, methods, and systems disclosed herein are prohibitedfrom being used with solvents other than ammonia as would be understoodby one of ordinary skill in the art, such use just may not be aspractical due to the predominant uses of the various other solvents.

EXAMPLES

The invention now will be described with respect to the followingexamples; however, the scope of the present invention is not intended tobe limited thereby.

Example 1

In a controlled laboratory setting, 12 microliters of the commercialproduct marketed as “KeyAcid™ Rhodamine WT” and manufactured by KeystoneAnaline Corporation of Chicago, Ill., which is a 21.2% w/w solution ofrhodamine WT in water, and 300 mL of anhydrous ammonia were combined ina flask. This is approximately equivalent to 2 oz of KeyAcid™ RhodamineWT in one ton of liquid anhydrous ammonia. The mixture was stirred untila solution formed that had a very slight yellow tint. The solvation ofrhodamine WT in ammonia transformed the rhodamine WT into a nearlycolorless composition. The surface of each piece of equipment used inthis process, however, was visibly stained a light pink in areas exposedto the ammonia and from which the ammonia had evaporated. The solutionwas also purposefully put in contact with various additional equipmentand materials, including metal screwdriver heads, concrete, and paper.All exposed equipment and materials were visibly stained pink uponevaporation of the anhydrous ammonia. During the mixing process, some ofthe mixture unintentionally contacted items, including protective glovesand the hands of the researchers who were performing the mixing. Theseadditional items were also visibly stained pink.

The solution of dye in ammonia was added to 2 grams of purepharmaceutical grade ephedrine in a 500 mL beaker. The contents of theflask were stirred to dissolve the ephedrine. Any material that cameinto contact with this solution, including the flask when the flask wasemptied, was also visibly stained pink upon evaporation of the ammoniasolvent. The visible pink stain on the flask was transferred to a spongewhen the flask was washed.

Lithium metal was added to the ephedrine solution. This mixture washeated to carry out a so-called “Birch” reaction. During the Birchreaction, materials contacted by the mixture were not stained. It isbelieved that the lack of a stain at this stage may be due to areduction of the rhodamine WT to a colorless composition.

Evaporation of the ammonia from the Birch reaction mixture left a freebase form of methamphetamine. In order to purify it, the free basemethamphetamine was dissolved into a liquid ether and converted to thehydrochloride salt by bubbling hydrogen chloride gas through thesolution. The methamphetamine salt precipitated from solution. Duringthis process plastic tubes used to carry the hydrogen chloride gas intothe dissolved methamphetamine were visibly stained pink as was thebeaker.

The methamphetamine salt product was filtered through a coffee filter toretain the methamphetamine. The coffee filter used for this filtrationalong with the resultant product is shown in the picture of FIG. 3. Twothings were observed. First, the coffee filter and resulting product areboth stained pink. Further, the filtration does not occur easily becauseinstead of a rapidly-drying, clear crystal being formed, the product wasa pink sludge, which was difficult to filter and dry. This pink sludge(methamphetamine) visibly stained objects with which it came intocontact pink, including plastic storage bags.

Example 2

A researcher's living human skin was exposed to a small amount of asolution of rhodamine WT and was visibly stained pink. The skin was thenrepeatedly washed until the dye was no longer visible to the unaidedhuman eye. The skin was then observed under irradiation by a hand-heldUV light which showed the originally stained area still indicated byfluorescence. Fluorescence was still visible on the skin two weeks laterwhen exposed to UV light after normal activity and washing by theresearcher. When a more concentrated solution of the dye was used in asimilar fashion, fluorescence was still visible 4-6 weeks afterexposure.

Example 3

Methamphetamine was generated using liquid anhydrous ammonia containingrhodamine WT as a dye in a similar manner to that discussed inExample 1. Physio-chemical investigation of the methamphetamine led to afinding that some dye resided on the outer surface of methamphetaminecrystals. To attempt to remove the dye from the resultantmethamphetamine, the crystals were washed with one of: water, acetone,toluene, petroleum ether or xylenes. In all cases either themethamphetamine and dye dissolved in the washing agent and the resultantmixture would stain objects it came into contact with, or neither themethamphetamine nor dye dissolved. The methamphetamine was recrystalizedfrom various solutions containing dyed methamphetamine and at least oneof: alcohol, toluene, xylenes and petroleum ether. The resultingrecrystalizations still showed obvious staining from the dye indicatingthat dissolution and recrystalization did not result in removal of thedye.

While the invention has been disclosed in connection with certainpreferred embodiments, this should not be taken as a limitation to allof the provided details. Modifications and variations of the describedembodiments may be made without departing from the spirit and scope ofthe invention, and other embodiments should be understood to beencompassed in the present disclosure as would be understood by those ofordinary skill in the art.

1. A solution for detecting the prior presence of liquid-state ammoniathe solution comprising: liquid anhydrous ammonia; and a rhodamine dyedissolved in said liquid anhydrous ammonia to form an ammonia solution;wherein said rhodamine dye will leave a stain on materials which were incontact with said ammonia solution upon conversion of some of saidammonia to a gas.
 2. The solution of claim 1 wherein said stain is apredetermined color visible to the human eye under illumination byvisible light.
 3. The solution of claim 2 wherein said solution is notsaid predetermined color.
 4. The solution of claim 1 wherein saidanhydrous ammonia is stored under pressure.
 5. The solution of claim 1wherein said dye comprises a colored dye.
 6. The solution of claim 1wherein said dye comprises a fluorescing dye.
 7. The solution of claim 1wherein said dye comprises a xanthene dye.
 8. The solution of claim 1wherein said dye comprises a rhodamine dye.
 9. A method of enabling thedetection of the prior presence of liquid-state ammonia comprising:introducing a dye into liquid-state ammonia to create a blend, said dyecreating a stain on materials in contact with said blend upon theconversion of said ammonia from a liquid to a gas; and storing saidammonia and dye in a pressurized tank.
 10. A method of deterring thetheft of anhydrous ammonia comprising: providing a sealed container ofanhydrous ammonia; and affixing a label to said sealed container, saidlabel indicating that said anhydrous ammonia includes a dye that willleave a detectable stain on objects that contact the anhydrous ammoniabut which is not readily visible in said anhydrous ammonia; wherein saidanhydrous ammonia does not include said indicated dye.
 11. The method ofclaim 10 wherein said label indicates that said anhydrous ammoniaincludes a dye that will stain a controlled substance produced usingsaid anhydrous ammonia.